Production of chlorinated bicyclic hydrocarbons



matter, the method"-for"producing same,

'fIl. is also 'stabledo ac'idicahd f'ailcalin allowing for awide'rangegof'torrnu-lati "or in conjunction with th 'dhexachloro=bicyclo; [2; .'1 ""ance-fwith thepres'ent inventto Ireacting,hexachlorocyclopentadien an 'fresiiltin thejnovelfinterni e"bicycle-[22:1,]-

" ration of the heptachlbrofint'ermediate: I

'monucnosaorcntx -nvnnoezrnnons- 4 cats" (Cuzco-64s This application isacont'inuation-in-part t copending April 18, .1950, and

application Serial No. 156,716, filed The present -invention fantasiaintermediate therefor. "More i rucuiany r vention relates to tlieproduction'ofiafnoveFchlormated,

bicyclic, dienic hydrocarbon andjits meanest e. l

The dienic product of the present "invention usefulas a pesticideinitselfa'nd also-intlieprparation ofiother valuable and potentpesticides. Thus, this compound'ex- 'hibits. fungicidal andinsecticidalactivitywithofit concomitaut phytotoxitythereby instiriusareusage lan U 'ereby The dienic product i .hw s halogenated to prodtieproduct- V e i The following isalsp ecific exafriplef'showing the prepapentadiene having a purity of approximately 90% Gaseof the reactingliquid was maintainedat 120- *2 .C. The

reaction was discontinuedafter 48 hours, and the reaction 'solution' wasfractionated. to separate unchanged; hexal i'atented Feb. 16,1960

p v. w

. ji ell D elormei Q-Cmra y, I

structural formula: 7

i specific T process shown" in the. fore goin'geiraniple Y maybevaried'with respect to conditions utilized.

The temperature of reaction may be withinthe range --of"about l00 toabout 200 .C. 1 The pressure inaclosed reactionvessel will necessarilyvary with-the temperature employed since one of the reactants is mrmangaseous.

-.:Elevated pressures are' desirable. in view. of the fact that one moleof product-is formed fro m 2 moles of reactants.

v the pressure The reaction may be carried out. at atmospheric pressures, for example by bubbling the gaseous reactant through the heatedliexachlorocyclopentadiene in aliquid Phase The :rate of reaction willvary with the temperature and employed, and will usually require tour;or

' more.ho urs. A lesser. time than is required for reaction completionwill still result in-the desiredproduct, but is uneconomical.

The product produced .is .a. l: 1 adduct of the twov reae tan.Consequently a mole ratio. of reactants; is

r THeptaclilorbbicyclohepterie (product ot Eriamplef-I) Ous vinylchloride in thetreaction vessel was'maint-ained was t Fatcd. .wlthethanollc potassium hydroxideisolutton at 2 atmospheres (absolutepressure) and the temperature desirable. However, the gaseous componentcan be em+ ployed in alesser proportion than 1:,1 mole ratio with afconstant ,replenishment, thereof as the reaction, ensues. t z xs sieash qm n m yq' w tai T frs ig 'qa sa c m l shsd .inn' ea a r ela tivelyinert solycntundertheiconditions utilizedrhowever, sincehergachlorocyclopentadieneis itselii'a liquidQthe ;i1s:e of suchadditional solventisl-not necessary, I 4 Y fWhen vinyl bromide isused inplace of the vinyl chloh m h fo e in qx m lemndsr essentially t d i n j..a 1 :t0 'h xa c g sntadie same . I beI-f9 l9wi -1 i su m d-Pre inhfhex V t I V chlorobicycloheptadiene from: the; productof Example I:'A'3-1ifer flask equippedwith: spars ri a er n f Y eter was charge with2,550 grams ofthexalclilorocycloat" the reflux temperature of ethanolfor approximately 4 7 hours; the solution contained 3 moles of potassiumhydroxidefor 'each mole'of the 'chloro compound present jtherein and itsconcentration with respect to potassium [hydroxide was approximately '3molar. The reaction mixture became very dark and inorganic salts-werethrown out of solution. These salts were separated on a filterchlorocyclopentadiene. A second fraction, which solidi fied in thereceiver, boiling between C. was also collected. This fractionwa smelted. and transferred to with-decolorizing charcoal at the boilingpoint of the solution; the methanol was completely evaporated from: thesolution and thecrystals which resulted wereair dried.

In this way 694.5 grams of ,a 125-136 C. was recovered.

product melting between and most of the ethanol. was removedQhyevaporation,-

' from theremaining solution. The concentrated solution which resultedwas stirred into water and the mixture was acidified with hydrochloricacid. Most of the water was decanted fromthe resulting .two-phasemixture and the' residue was extracted'with diethylether. This-stepin'the- ,.process resulted in the" formation of anemulsion which]separated 0nly,,slowly.' The separatede'therphase was" 7 ;dried overanhydrous sodium'sulfate and the ether was Analysis-Calculated for cmcmcar'bon', 25.07%; hydrogen, .86%; chlorine, 74.1%.- Foundz- Carbon;

25.5%; hydrogen, .86%; chlorine, 74.1, 74.4%.

The compound thus obtained is the adduct of hexachlorocyclopentadienewith vinyl chloride, 1,2,3,4,5,7,7-

evaporated, leaving a black, oily material. This black oily material wasdistilled in vacuo and the cut boiling..be-.

f tween 128-145 C. at 18 rnmLHg abs.,was collected.

The material-in this fraction represented a yield of ap proximately78%based on the. amount of ,bicycloheptene taken for reaction.

-Analysis.--Calculated for C H Cl hydrogen, 0.67%. 0.81%.. Q

heptachlorovinyljbromidedsobtained, ;vnam ely, 5-bromo 1,2,3,4,

Carbon, 28.1%; Found: Carbon, 285%; hydrogen, a

The compound thus obtained is 1,2,3,4,7,7-hexachlor o- H bicyclo(2.2.l)-2,5-heptadiene represented by the structuralformula:

C] J: H 01 01' c1 H or The pure compound obtained by fractionaldistillation in vacuo has the following physical characteristics Themelting point is about -4 C., the density (11 is i 1.664,g./ml. and therefractive index (11 is 1.5529.

The product boils at a temperature of about 75 C. at 0.4

mm. mercury pressure (absolute) and at about 149C.

I (with decomposition) at 30 mm. mercury pressure (absolute). p 7 I pThis compound is also obtainable by the similar dehydrohalogenation-(dehydrobro mination) of -bromo- 1,2,3,4,7,7hexachloro-bicyclo-(2.2.l)-2-hep-teneby the use of alcoholic potassiumhydroxide in essentially the In additign, the present compound is veryvaluable as an intermediate in the preparation of the valuableinsecticides known as 711 and .269 which are respectively the.

adduct of the present compound with cyclopentadiene and the 6,7 epoxidether eqfde scribedand claimed respectively in the copending applicationsof Rex E. Lidov, Serial;No;-'-325,881, filed December 13, 1952, and nowus'P-atent 2,717,851, and Henry Bluestone, Serial No.

156,716 filedApril, 18, 1950 and now Us. Patent 2, 76,132:

I claim as r ny'invention: 7 1 A compound having the formula:

I 2.Th'e method of 'forming 1,2,3,4,7,7-hexachlorobicycle-(2.2.1)-2,51heptadiene which comprises reactingsame manner as it was obtained in Example 11 from the.

, heptachlorobicycloheptene,

v The dehydrohalogenation reaction may be carried out by using otheralkali metalhydroxides such as sodium solvent used. The ratio ofQuantity of alkaline material to the organic reactant may vary betweenabout stoichisuch as 3 to 6' moles or more per mole of organic reactant.

The new dienic composition of this invention has many uses other thanthose already enumerated. 3 Thus, it can be used as a plasticizer andtackifierin man yresinous compositions as well as 'an impregnant andfire-proofing agent in view of its high degree of halogenation.

preferred .a' vinyl halide of the group consisting of vinyl-chloride andvinyl. bromide with hexachlorocyclopentadiene in a Diels-Alder manner toform their .equi-molar adduct, and dehydrohalo-genating said adductbyreacting it with an alkali metal hydroxide in the presence of-asolvent selected from the group consisting of lower alkanols andethanol, such as methanol, propanol, butanol, dioxane',"- dloxane 3. Themethod of [forming l,2,3 ,4,7,7-hexac hlorobicycle-(2.2.1)-2,5heptadiene which comprises dehydrohalogenating l,2,3,-4,5,7,7heptachloro-bicyclo-(2.2;1)-2- 1 heptene by reacting it with an alkali:rneta l hydroxide in sisting of lower alkanolsanddioxane.

the presence of a.-solv ent selected from the group con v4. The methodor I forming 1,2-,3,4,7,7.-hexachloro- .bicy clo(2.2.l) 2,5-heptadienewhich comprises dehydrohalogenating .5-brorno 1,2,3,4,7,7.-hexachloro-bicycld ometric quantities or even less to large excessthereof This composition is also valuable as astarting compound in thepreparation of perfumes, medicinals, and other organic compounds usefulin the artsand sciences.

(2.2.1.) -2- heptene by reacting itwith an alkali metal hydroxide in thepresence ofasolvent selected from the group consisting of loweralkanolsand dioxane.

References Cited in the file of this patent V i Q MiIQ 498,176 BelgiumOct. 14, 1950 OTHER REFERENCES Krynitsky et a]: "Jo'ur. Cheni. Soc. vol.I 69, pp.

1. A COMPOUND HAVING THE FORMULA:
 3. THE METHOD OF FORMING1,2,384,7,7-HEXACHLOROBICYCLO-(2.2.1)-2,5-HEPTADIENE WHICH COMPRISESDEHYDROHALOGENATING 1,2,3,4,5,7,7 - HEPTACHLORO-BICYCLO-(2.2.1)-2HEPTENEBY REACTING IT WITH AN ALKALI METAL HYDROXIDE IN THE PRESENCE OF ASOLVENT SELECTED FROM THE GROUP CONSISTING OF LOWER ALKANOLS ANDDIOXANE.